KR100649439B1 - Photocurable resin composition and resin composition for plastics comprising the same - Google Patents

Abstract

This invention contains (A) cationically polymerizable compound, (B) acrylic resin, (C) photocationic polymerization initiator, (B) acrylic resin has a cationically polymerizable functional group, and sums of (A) and (B) (A) is 30-95 weight part and (B) is 5-70 weight part in 100 weight part, It is related with the photocurable resin composition. The functional group of the acrylic resin (B) preferably contains any one or more of a cyclic ether group, a vinyloxy group, an acid addition product of a vinyloxy group, and an active hydrogen group, and more preferably an active hydrogen group is a hydroxyl group.

ADVANTAGE OF THE INVENTION According to this invention, the photocurable resin composition which has sufficient photocurability and has sufficient adhesiveness with respect to the hard plastic represented by polycarbonate and PET which are hard-adhesive can be obtained.

Description

Photocurable resin composition and resin composition for plastics comprising the same {Photocurable resin composition and resin composition for plastics comprising the same}

This invention relates to the photocurable resin composition used for the coating material, adhesive agent, ink, etc. which are hardened by light irradiation. In particular, it is used for hard-adhesive hard plastics, such as polycarbonate, PET, and ABS resin.

Recently, plastic materials have been widely used in the field of electronic information materials. For example, polycarbonates, which are hard plastics, are often used for cellular phones and optical disks. Similarly, PET resin is used for the optical film, and ABS resin is used for the housing | casing of home appliances information equipment. In the process of these products, although there exists a process of bonding, painting, and printing these hard plastics by photocuring, all these materials are hard-adhesive. In addition, it is desired to provide high adhesion to the base resin to materials used for coatings, adhesives, inks and the like.

As one of the methods of providing high adhesiveness, when hardening a base resin, the method of reducing the residual stress which generate | occur | produces in an adhesive interface by low hardening shrinkage is known to be effective. As a method of realizing this low cure shrinkage, from the cure system using the addition polymerization by radical photopolymerization using the conventional acrylic monomer, etc., it is used for the photocationic ring-opening polymerization of cyclic ethers, such as epoxy resin and oxetane resin, with small cure shrinkage. Curing system was proposed. However, this curing system using photo cationic ring-opening polymerization is difficult to introduce a functional group capable of interacting with the hard plastic as the adherend and could not sufficiently provide adhesion.

Therefore, in the photocationic ring-opening polymerization system composed of an epoxy compound, an oxetane compound, a photocationic polymerization initiator, a pigment as a colorant and a pigment dispersant, a comb polymer having an anchor as a pigment dispersant and a liquid at room temperature is an active ingredient. By the addition, the adhesive expression with the adherend was attempted to express sufficient adhesiveness (for example, Patent Document 1). However, since this system contains a basic substance which can be a retarder in the polymerization reaction of photo cationic ring-opening polymerization, it has a drawback in that it cannot express a sufficient curing rate necessary for productivity.

[Patent Document 1]

JP 2003-212965 A

It is providing the photocurable resin composition which has sufficient photocurability, and has sufficient adhesiveness with respect to the hard plastic represented by polycarbonate and PET which are hard-adhesive.

MEANS TO SOLVE THE PROBLEM As a result of earnest examination, the inventors added the specific acrylic resin which provided the cationically polymerizable functional group to the photocationic polymerization system which consists of cationically polymerizable compounds, such as an epoxy compound and an oxetane compound, and a photocationic polymerization initiator at the time of hardening, It discovered that sufficient hardenability and adhesiveness were expressed, and came to complete this invention.

That is, the present invention

(A) Cationically polymerizable compound, (B) Acrylic resin, (C) Photocationic polymerization initiator containing, (B) Acrylic resin has a cationically polymerizable functional group, 100 weight part of total of (A) and (B) (A) is 30-95 weight part and (B) is 5-70 weight part in the photocurable resin composition.

The functional group of the acrylic resin (B) preferably contains any one or more of cyclic ether groups, vinyloxy groups, acid addition products of vinyloxy groups, and active hydrogen groups, and more preferably the active hydrogen groups are hydroxyl groups. Moreover, it is preferable that the weight average molecular weight (polystyrene conversion) of (B) acrylic resin is the range of 1,000-100,000.

The cationic polymerizable compound (A) preferably contains a cyclic ether group, and more preferably contains an epoxy group and / or an oxetanyl group.

Moreover, this invention is a coating composition, adhesive composition, and ink composition for plastics containing the photocurable resin composition mentioned above.

This invention is demonstrated in detail below.

[(A) Cationically Polymerizable Compound]

The (A) cationically polymerizable compound component used in the present invention has at least one cationically polymerizable functional group in the monomolecular chain. Specifically, compounds having cyclic ethers such as oxirane ring, oxetane ring and tetrahydrofuran ring in the molecule, cyclic formal, cyclic carbonate, cyclic ester, vinyloxy, cyclic thioether (thiirane), The cyclic olefins and styrenes are not particularly limited as long as they have cationically polymerizable properties. Among these, a compound having an epoxy group or a compound having an oxetanyl group is preferable. At this time, you may contain an epoxy group and an oxetanyl group simultaneously.

<Epoxy Compound>

Specifically, a compound containing an epoxy group is exemplified. Specific examples of the compound having one epoxy group include phenylglycidyl ether and butylglycidyl ether, and the compound having two or more epoxy groups is hexanediol di. Glycidyl ether, tetraethylene glycol diglycidyl ether, trimethylol propane triglycidyl ether, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, novolak glycidyl ether, hexahydrophthalic acid glycine Dyl esters, Dimer acid glycidyl esters, tetraglycidylaminodiphenylmethane, 3,4-epoxy-6-methylcyclohexylmethylcarboxylate, triglycidyl isocyanurate, 3,4-epoxycyclohexylmethyl Glycidyl ethers such as carboxylate, polypropylene diglycidyl ether, polybutadiene or polysulfide sock end diglycidyl ether modifications; and the like can be given. Moreover, alicyclic epoxy, such as 3, 4- epoxycyclohexyl methyl-3, 4- epoxy cyclohexane carboxylate and bis- (3, 4- epoxy cyclohexyl) adipate, is also mentioned.

Moreover, the compound which has a functional group as represented by General formula (1) as a cyclic ether of a three-membered ring like an epoxy group is also provided as component (A) of this invention.

……(1)

… … (One)

In General Formula (1), R ₁ And R ₂ is a carbon atom, and the carbon atom is saturated or unsaturated. R ₃ is a hydrogen atom or a carbon atom, and the carbon atom is saturated or unsaturated.

Compounds having an oxirane ring group represented by at least one general formula (1) in a single-molecular chain include one carbon atom substituted with at least one hydrogen atom among carbon atoms constituting the oxirane ring, and the other carbon atom is 2 Substituted carbon atoms, and the substituted carbon atom is a compound having at least one oxirane cyclic group represented by the general formula (1) in the one-molecular chain, which is a saturated bond or an unsaturated bond. In addition, the saturated or unsaturated bond of this carbon atom may be substituted by arbitrary atom groups.

Specifically, R ₁ and R ₂ represent a hydrocarbon composed of any one of alkanes, alkenes, and alkynes and may have a substituent. Examples of the substituent include an alkyl group, a cycloalkane, an aromatic ring, a halogen, a hydroxyl group, an ether, an aldehyde, a ketone, an ester group, an alkyl substituted amide group, and an alkyl substituted amino group, but are not particularly limited. In addition to R ₃ , R ₃ represents a hydrocarbon composed of any of alkanes, alkenes, and alkynes and may have a substituent. Examples of the substituent include an alkyl group, a cycloalkane, an aromatic ring, a halogen, a hydroxyl group, an ether, an aldehyde, a ketone, and an ester group, but are not particularly limited.

More specifically, examples of the compound having an oxirane ring group represented by at least one general formula (1) in one molecule chain include terpinolene dioxide, isobutylene oxide, isoprene oxide, β-pinene oxide and 2- Methylglycidol, limonene dioxide, methyl 2-methylglycidate, 7-oxa-bicyclo [4.1.0] heptanooxyranyl, 2-acetyl-2-methyloxirane, 2- (benzyloxymethyl) -2 -Methyloxirane, 5,6-epoxy-4,7-methano-1-oxaspiro- (2,5) -octane, 2-methyl-1- (2-methyl-oxyranyl) -non-3- En-1-ol, myrcene dioxide, etc. are mentioned. In particular, terpinolene dioxide, limonene dioxide or 7-oxa-bicyclo [4.1.0] heptaneoxyranyl, 5,6-epoxy-4,7-methano-1-oxaspiro- (2,5) -octane Since at least one or more unique oxirane ring structures represented by the general formula (1), such as or myrcene dioxide, may be present in a molecule, it is also possible to have a structure having cationically polymerizable properties such as other oxirane rings in the same molecule. none.

<Oxetane compound>

Specifically, a compound having an oxetanyl group is exemplified. Specific examples of the compound having one oxetanyl group include 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-phenoxymethyloxetane, 3 -Ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl (triethoxysilylpropoxymethyl) oxetane, 3-cyclohexyloxymethyl-3-ethyl-oxetane, etc. are mentioned.

Specific examples of the compound having two oxetane rings include bis (3-ethyl-3-oxetanylmethyl) ether and 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} Benzene and the like. Specific examples of the compound having three or more oxetane rings include trimethylolpropane tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritoltris (3-ethyl-3-oxetanylmethyl) ether, and pentaerythritol Tetrakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, and the like. Although these cationically polymerizable compounds may be used individually or in combination of 2 or more types, It is preferable to use together the compound containing an epoxy group, and the compound containing an oxetanyl group preferably.

[(B) Acrylic Resin]

The acrylic resin (B) used in the present invention is characterized by containing a cationically polymerizable functional group. That is, at the time of hardening by photocationic ring-opening polymerization, the component (B) acrylic resin reacts with unit (A) any one of unit reactions, such as start, growth, stop, and chain transfer in cationic polymerization. In, it is characterized in that it is introduced into the crosslink by covalent bonds.

About each unit reaction, a cyclic ether group can be used as a functional group which can become an initiation terminal in the initiation reaction of cation ring-opening polymerization. The cyclic ether group is added to the proton generated from the photo cationic polymerization initiator to produce an oxonium ion which can be the starting end. The present invention also provides a structure in which an acid is added to a vinyloxy group and a vinyloxy group, which are functional groups capable of producing carbo cations, also useful for ring-opening polymerization of cyclic ethers. Next, an active hydrogen group can be mentioned as a functional group which can be introduced as a chain transfer or a stop terminal, The hydroxyl group, a thiol group, an amino is mentioned as the active hydrogen group, A hydroxyl group is the most preferable. Next, the cyclic ether group mentioned above is mentioned as a functional group introduce | transduced by the growth reaction of cation ring-opening polymerization.

Although the functional group in each unit reaction is illustrated below, any reaction, such as said start, growth, stoppage, and chain transfer, should just be possible, and is not limited only to the functional group shown below. The raw material is generally commercially available, and it is preferable to contain any one or more of cyclic ether groups, vinyloxy groups, acid addition products of vinyloxy groups, and active hydrogen groups.

In the case of an active hydrogen group, Preferably it is a carboxylic acid, a hydroxyl group, a thiol group, an amino group, More preferably, it is a hydroxyl group. The hydroxyl group may be either an alcoholic hydroxyl group or a phenolic hydroxyl group, but preferably an alcoholic hydroxyl group is preferable. Below, the introduction method of these functional groups is described.

In general, a method of introducing a functional group into an acrylic resin includes a method of introducing a functional group into the polymer side chain by radical copolymerization of a radical polymerizable monomer having a functional group with another radical polymerizable monomer, or 2,2'-azobis (2- A radical polymerization initiator having a functional group in an initiator fragment such as hydroxymethylpropionitrile) or a chain transfer agent having a functional group such as thiodiglycol can be introduced at the molecular end of the polymer. Below, it demonstrates concretely about the radically polymerizable monomer which has a functional group mentioned above.

As a radically polymerizable monomer which has a cyclic ether group in a side chain, the (meth) acrylate monomers which have a cyclic ether group in a side chain are mentioned, More specifically, glycidyl (meth) acrylate which has a glycidyl group, jade 3-ethyl-3-oxetanylethyl (meth) acrylate having a cetanyl group, 3,4-epoxycyclohexylmethyl (meth) acrylate having an alicyclic epoxy group, methyl glycid having a substituted methyl group in the glycidyl group The dimethacrylate, the tetrahydrofurfuryl (meth) acrylate which has a tetrahydrofuran ring, etc. are mentioned.

As a radically polymerizable monomer which has a vinyloxy group in a side chain, 2- (vinyloxyethoxy) ethyl (meth) acrylate which has an acryloyl group and a vinyloxy group in 1 molecule is mentioned. The present invention also provides a structure in which an acid such as acetic acid, trifluoroacetic acid and hydrochloric acid is added to the vinyloxy group. As a radically polymerizable monomer which has a hydroxyl group in a side chain, ring-opening addition of (epsilon) -caprolactone of 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and 2-hydroxyethyl (meth) acrylate A hydroxyl group should just exist in a side chain, such as water, the mixture of ethylene oxide and / or propylene oxide of (meth) acrylic acid ester, and / or a single adduct, and there is no restriction | limiting in particular. Furthermore, it is potentially a hydroxyl group by an acid catalyst or the like such as a (hemi) acetal structure such as (2-methyl-2-ethyl-1,3-dioxolan-4-yl) methyl (meth) acrylate, a benzyl group, and a tert-butyl group. A functional group for generating is also provided in the present invention.

The acrylic resin (B) generally refers to a copolymer of a radical polymerizable monomer having a functional group in the side chain and another radical polymerizable monomer. (Meth) acrylates are mentioned as another radically polymerizable monomer. As ester groups of these (meth) acrylates, methyl group, ethyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, 2-ethylhexyl group, cyclohexyl group, benzyl group and isoboro It is preferable to have a nonfunctional alkyl ester, regardless of linear or branched structures, such as a silyl group, a lauryl group, and a myristyl group. Moreover, what can be copolymerized with (meth) acrylates, such as styrene, (alpha) -methylstyrene, and vinyl acetate, can be used as a monomer which comprises (B) of this invention.

The radically polymerizable monomer having the functional group described above and the other radically polymerizable monomer are obtained as a copolymer by radical polymerization in an organic solvent using an organic peroxide or an azo compound as a radical polymerization initiator, but may be used as it is. It is obtained as an acrylic resin by desolving a solvent powder from the resin liquid containing the solvent containing this copolymer, and is used as (B).

(B) Although acrylic resin contains a cationically polymerizable functional group, the content is 1-50 weight% normally in (B) from a sclerosis | hardenability viewpoint, Preferably it is 1-30 weight%. In addition, the weight average molecular weight (polystyrene conversion) by gPC of the (B) acrylic resin used for this invention is 1,000-100,000 from a viewpoint of durability and adhesiveness, Preferably it is 1,000-50,000.

[(C) Photo cationic polymerization initiator]

The (C) photocationic polymerization initiator used for this invention is a compound which generate | occur | produces a cationic species or Lewis acid by light.

Onium salt compounds that generate cationic species or Lewis acids by active energy rays include diphenyliodonium, 4-methoxydiphenyliodonium, bis (4-methylphenyl) iodonium, and bis (4-tert-butyl Phenyl) iodonium, bis (dodecylphenyl) iodonium, triphenylsulfonium, diphenyl-4-thiophenoxyphenylsulfonium, bis [4- (diphenylsulfonio) -phenyl] sulfide , Bis [4- (di (4- (2-hydroxyethyl) phenyl) sulfonio) -phenyl] sulfide, eta 5-2,4- (cyclopentadienyl) [1,2,3,4, Onium ions such as 5,6-η- (methylethyl) benzene] -iron (1+), tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate, hexafluoroarsenate, hexachloro The compound which consists of combinations of anions, such as an antimonate, is mentioned. Further, onium salts which generate cationic species or Lewis acids by commercially available active energy rays include Uvacure 1590, 1591 (above, manufactured by DAICEL-UCB Company, Ltd., trade name), San-Aid SI-110, and SI-180. , SI-100L, SI-80L, SI-60L (above, manufactured by Sanshin Chemical Co., Ltd.), Adeka Optomer SP-100, SP-172, SP-170, SP-152 (above, made by Asahi Denka Co., Ltd., Trade name), 2074 (manufactured by Rhodia, trade name), and the like.

The above photo cationic polymerization initiators may be used alone or in combination of two or more kinds thereof. A sensitizer, such as thioxanthone and 2-ethyl anthraquinone, can also be added and used. Moreover, it is also possible to superpose | polymerize using an active energy ray and heat together.

The above (A), (B), and (C) express even more excellent curability and adhesiveness at a specific compounding ratio. That is, in 100 weight part of (A) and (B) in total, it is (A) 30-95 weight part, (B) 5-70 weight part, Preferably (A) 50-95 weight part, (B) 5 to 50 parts by weight. If the compounding quantity of (A) and (B) exists in this range, it is preferable from a viewpoint of adhesiveness and sclerosis | hardenability. In addition, the compounding quantity of (C) is 0.5-10.0 weight part with respect to a total of 100 weight part of (A) and (B). If the compounding quantity of (C) exists in this range, it is preferable from a viewpoint of sclerosis | hardenability, water resistance, the coloring problem of resin, etc.

Other resin can be used for the composition of this invention as needed. As other resin components, for example, polybutadiene, polychloroprene, polyether, polyester, styrene-butadiene-styrene block copolymer, petroleum resin, xylene resin, ketone resin, cellulose resin, fluorine oligomer, silicone oligomer, polysulf Feed oligomers, etc. are mentioned. You may use these individually or in combination of many types.

As a modifier, a polymerization initiator (photosensitizer), an anti-aging agent, a leveling agent, a wettability improving agent, an adhesive agent, surfactant, a plasticizer, a light absorbing agent, etc. are mentioned, for example. You may use these individually by 1 type or in combination of many types. Diluents can be used to impart or improve applicability. As a diluent, the usual organic solvent and the above-mentioned monofunctional cyclic ether are used.

Since this invention is a photocurable resin composition which has sufficient photocurability, and has sufficient adhesiveness with respect to the hard plastics which are hard-adhesive polycarbonate and PET, it can be used for the coating composition of these plastics. It can also be used for adhesives, ink binders and the like. Moreover, it can use for the material for optical disks which require high precision adhesiveness and coatability, especially a protective coating agent and the adhesive agent for optical disks.

[ Example ]

Hereinafter, an Example and a comparative example demonstrate this invention concretely. In addition, about curability and adhesiveness, the Example and the comparative example were evaluated with the following method.

(Curable)

The photocurable resin composition was applied on a polycarbonate plate and a polyethylene terephthalate (PET) plate (4.5 cm × 2.0 cm × 0.2 cm) using an applicator at 100 μm, irradiated with 1 J / cm 2 with a metal halide lamp, and immediately after irradiation The degree of curing of the coating film on the surface of the polycarbonate plate was evaluated visually. The degree of curing was set to x for those having cured and no tack, those having cured only the surface, or those having adhesiveness on the surface, and no cured at all.

(Adhesiveness)

The photocurable resin composition was applied on a polycarbonate plate and a polyethylene terephthalate (PET) plate (4.5 cm × 2.0 cm × 0.2 cm) at 100 μm using an applicator and irradiated with 1 J / cm 2 with a metal halide lamp. The coating film was subjected to the adhesion test with 25 grids of 2 mm square in accordance with JIS K5400 8.5.2. Moreover, this test piece was preserve | saved for 100 hours in the 85 degreeC x 80% constant temperature and humidity tester, and the adhesive test was done again.

[Production Example 1]

Under nitrogen, 340.0 g of xylene was placed in a 2L acrylic resin composition production apparatus equipped with a stirrer, a thermometer, a reflux condenser, a dropping tank, and the like, followed by heating up to a polymerization temperature of 135 ° C. To this, a mixture of 400 g of methyl methacrylate, 50 g of styrene, 50 g of 2-hydroxyethyl methacrylate and 20 g of tert-butyl2-ethylhexanoate as a radical initiator was added dropwise over 4 hours. After completion of the dropping, stirring was continued at 135 ° C for 1 hour. Subsequently, xylene and the residual monomer were distilled off by making this manufacturing apparatus into a vacuum, and (B) acrylic resin was obtained.

[Production Examples 2 to 6, 8]

It carried out similarly to manufacture example 1 except having changed the quantity of the radically polymerizable monomer and radical initiator shown in Table 1.

[Manufacture example 7]

It carried out similarly to the manufacture example 1 except having changed the quantity and polymerization temperature of the radically polymerizable monomer and radical initiator shown in Table 1 to 100 degreeC.

Example 1

In the light-shielding brown bottle, 10 parts by weight of the acrylic resin obtained in Production Example 1 as (B), 60 parts by weight of hydrogenated bisphenol A-type epoxy resin (manufactured by Asahi Denka Co., Adecar Resin EP-4080S) as (A) 30 parts by weight of di [1-ethyl (3-oxetanyl)] methyl ether (manufactured by Dong-A Synthetic Co., Ltd., Aaron Oxetane OXT-221) was added thereto, followed by heating and stirring to confirm that (A) and (B) became completely uniform. It was. Subsequently, when this mixed resin liquid became 60 degrees C or less, (C) 3 weight part of (tolyl cumyl) iodonium tetrakis (pentafluorophenyl) borate (RHODORSIL PHOTOINITIATOR 2074 made from Rhodia) was mixed as a cationic polymerization initiator. It melt | dissolved and obtained the photocurable resin composition.

Table 3 shows the results of evaluating the cationically polymerizable resin composition according to the above evaluation method.

[Examples 2 to 11]

Except having changed the kind and quantity of component (A), component (B), and component (C) shown in Table 2, it mix | blended similarly to Example 1, evaluated, and the result was shown in Table 3.

In addition, about Example 4, the adhesive test with the polyethylene terephthalate plate was done, and the result was shown in Table 4.

Comparative Example 1

In the light-shielding brown bottle, 70 parts by weight of hydrogenated bisphenol A type epoxy resin (manufactured by Asahi Denka Co., Adecarazine EP-4080S) and di [1-ethyl (3-oxetanyl)] methyl ether (A) 30 parts by weight of Aaroniaxetane OXT-221 manufactured by Dong-A Synthetic Co., Ltd. (C) 3 parts by weight of iodonium tetrakis (pentafluorophenyl) borate (RHODORSIL PHOTOINITIATOR 2074, manufactured by Rhodia) as a cationic polymerization initiator (tolylcumyl) It melt | dissolved and obtained the photocurable resin composition. This photocurable resin composition was evaluated in accordance with the above evaluation method, and the results are shown in Table 3.

Moreover, the adhesive test with the polyethylene terephthalate plate was done, and the result was shown in Table 4.

Comparative Example 2

68 parts by weight of hydrogenated bisphenol A epoxy resin (manufactured by Asahi Denka Co., Adecarazine EP-4080S) and di [1-ethyl (3-oxetanyl)] methyl ether (A) 3 parts by weight of Aaron Oxetane OXT-221) and 30 parts by weight of (C) cationic polymerization initiator (tolyl cumyl) iodonium tetrakis (pentafluorophenyl) borate (Rhodias, RHODORSIL PHOTOINITIATOR 2074) Mixed and dissolved. Here, the anchor disclosed in Japanese Patent Laid-Open No. 2003-212965 is a base, and a poly (ethyleneimine) -poly (1,2-hydroxystearic acid) graft polymer (Avecia Ltd.) is a comb-like polymer of liquid at room temperature. 2 parts by weight of Solsperse 28000) was prepared to obtain a photocurable resin composition.

Table 3 shows the results of evaluating the photocurable resin composition according to the above evaluation method.

Comparative Example 3

10 parts by weight of the acrylic resin obtained in Production Example 6 as a component (B) and a hydrogenated bisphenol A type epoxy resin (manufactured by Asahi Denka Co., Adecarazine EP-4080S) as a component (B) in a light-shielding brown bottle 60 Part by weight and 30 parts by weight of di [1-ethyl (3-oxetanyl)] methyl ether (manufactured by Dong-A Synthetic Co., Ltd., Aaron Oxetane OXT-221) were added to the mixture, followed by heating and stirring, so that (A) and (B) were completely uniform. Confirmed Subsequently, when this mixed resin liquid became 60 degrees C or less, (C) 3 weight part of (tolyl cumyl) iodonium tetrakis (pentafluorophenyl) borate (RHODORSIL PHOTOINITIATOR 2074 made from Rhodia) was mixed as a cationic polymerization initiator. It melt | dissolved and obtained the photocurable resin composition.

Table 3 shows the results of evaluating the cationically polymerizable resin composition according to the above evaluation method.

Preparation Example 1 Preparation Example 2 Preparation Example 3 Preparation Example 4 Preparation Example 5 Preparation Example 6 Preparation Example 7 Preparation Example 8 Functional group containing radically polymerizable monomer 2-hydroxyethyl methacrylate 10 5 10 10 Glycidyl methacrylate 10 5 3-ethyl-3-oxetanylethyl methacrylate 10 Methacrylic acid 2- (vinyloxyethoxy) ether 10 Nonfunctional Radical Polymerizable Monomer Methyl methacrylate 80 80 80 80 80 85 80 80 Styrene 10 10 10 10 10 15 10 10 Radical initiator tert-butyl2-ethylhexanoate 4 4 4 4 4 4 0.05 15 Weight average molecular weight (polystyrene equivalent) 12000 13000 11000 25000 13000 12000 200000 900

Example Comparative example Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Comparative Example 1 Comparative Example 2 Comparative Example 3 Ingredient (A) Ade car resin EP-4080S 60 60 60 60 60 30 30 60 60 15 65 70 68 60 Epoic R140 10 Epicoat 1007 10 Aaron oxetane OXT-221 30 30 30 30 30 30 25 30 30 15 30 30 30 30 Ade car resin KRM2110 10 β-pinene oxide 5 Ingredient (B) Preparation Example 1 10 40 10 Preparation Example 2 10 70 5 Preparation Example 3 10 Preparation Example 4 10 Preparation Example 5 10 Preparation Example 6 10 Preparation Example 7 10 Preparation Example 8 10 additive Solsperse28000 2 Ingredient (C) RHODORSIL PHOTOINITIATOR 2074 3 3 3 3 3 3 3 3 3 3 3 3 3 3

Evaluation item Example Comparative example Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Comparative Example 1 Comparative Example 2 Comparative Example 3 Curable ○ ○ ○ ○ ○ ○ ○ ○ ○ △ ○ ○ × ○ Adhesion Early 25/25 25/25 25/25 25/25 25/25 25/25 25/25 20/25 25/25 25/25 25/25 0/25 - 25/25 After accelerated test 25/25 25/25 25/25 25/25 25/25 25/25 25/25 20/25 20/25 25/25 20/25 0/25 - 0/25

Evaluation item Example 4 Comparative Example 1 Curable ○ ○ Adhesion Early 25/25 20/25 After acceleration test 25/25 15/25

The photocurable resin composition of this invention has sufficient sclerosis | hardenability, adheres to polycarbonate, PET, etc. which are hard-adhesive hard plastics, and can maintain the same adhesiveness even after an accelerated test. Moreover, when the photocurable resin composition of this invention is used, it can be used for the coating material, adhesive agent, ink, various sealing materials, etc. of members using hard plastics, such as polycarbonate and PET.

Claims (9)

(A) Cationically polymerizable compound, (B) Acrylic resin, (C) Photocationic polymerization initiator containing, (B) Acrylic resin has a cationically polymerizable functional group, 100 weight part of total of (A) and (B) In (A), 30-95 weight part and (B) are 5-70 weight part, The photocurable resin composition characterized by the above-mentioned. The photocurable resin according to claim 1, wherein the cationic polymerizable functional group of the acrylic resin (B) contains any one or more of cyclic ether groups, vinyloxy groups, acid addition groups of vinyloxy groups, and active hydrogen groups. Composition. The photocurable resin composition according to claim 2, wherein the active hydrogen group of the cationic polymerizable functional group of the acrylic resin (B) is a hydroxyl group. The photocurable resin composition according to claim 1, wherein the weight average molecular weight (polystyrene equivalent) of the acrylic resin (B) is in the range of 1,000 to 100,000. The photocurable resin composition according to claim 1, wherein the cationic polymerizable compound (A) contains a cyclic ether group. The photocurable resin composition according to claim 5, wherein the cationic polymerizable compound (A) contains an epoxy group and / or an oxetanyl group. The coating composition for plastics containing the photocurable resin composition of any one of Claims 1-6. The adhesive composition for plastics containing the photocurable resin composition of any one of Claims 1-6. The ink composition for plastics containing the photocurable resin composition of any one of Claims 1-6.